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Cite this: Catal. Sci. Technol., 2012, 2, 1455–1462

www.rsc.org/catalysis PAPER
Photocatalytic oxidative desulfurization of dibenzothiophene under
simulated sunlight irradiation with mixed-phase Fe2O3 prepared by
solution combustionw
Fa-tang Li,*a Ying Liu,a Zhi-min Sun,a Ye Zhao,a Rui-hong Liu,a Lan-ju Chena
and Di-shun Zhaob
Published on 24 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CY00485B

Received 25th November 2011, Accepted 6th March 2012

DOI: 10.1039/c2cy00485b

Mixed-phase Fe2O3 was prepared from Fe(NO3)3 and (C2H5)3NHCl via solution combustion.
Photocatalytic oxidative desulfurization of dibenzothiophene (DBT) under simulated sunlight
irradiation using mixed-phases of a- and b-Fe2O3 as catalysts was investigated. The DBT in the
oil phase was extracted into water phase and then photooxidized to CO2 and SO42 by Fe2O3 and
O2 dissolved in water. The Fe2O3 containing 36.6% b-Fe2O3 and 63.4% a-Fe2O3 exhibited the
Downloaded on 05 October 2012

highest photocatalytic activity. Sulfur removal of DBT in n-octane was 92.3% for 90 min
irradiation under the conditions of V(water) : V(n-octane) = 1 : 1, air flow rate at 150 mL min 1,
and Fe2O3 addition at 0.05 g. The kinetics of photooxidative desulfurization of DBT was a
pseudo-first-order with an apparent rate constant of 0.0287 min 1 and half-time of 24.15 min.
The sulfur content of the actual diesel could be reduced from 478 mg mL 1 to 44.5 mg mL 1 after
90 min. The radical scavengers experiments and terephthalic acid fluorescence technique indicated
that  OH and O2 were the main reactive species in the DBT photocatalytic degradation.
A potential photocatalytic desulfurization mechanism using mixed-phase Fe2O3 was proposed.

1. Introduction These are highly polarized compounds, which can be removed

Deep desulfurization of fuel oils has received increasing global
attention because of the emergence of stringent sulfur content
protocols. Conventional catalytic hydrodesulfurization is
highly efficient in removing thiols, sulfides, and disulfides.
However, this approach is less effective for dibenzothiophene
(DBT), and DBTs having alkyl substituents on their 4- and/or
6-positions.1,2
Oxidative desulfurization (ODS) has attracted much attention
as an alternative technology due to its high efficiency, low cost,
and moderate operation conditions.3–8 As a kind of ODS
technique, photocatalytic ODS is also attracting interest.
Under this photocatalytic ODS process, sulfur compounds
can be photooxidized to CO2, SO42 , sulfoxides, and sulfones.
a
College of Science, Hebei University of Science and Technology,
Shijiazhuang 050018, China. E-mail: lifatang@126.com;
Fax: +86-311-81668512; Tel: +86-311-81669971
b
College of Chemical and Pharmaceutical Engineering,
Hebei University of Science and Technology,
Shijiazhuang 050018, China
w Electronic supplementary information (ESI) available: Schematic
diagram of photochemical reactor (Fig. S1), ESI-MS spectra of
solution (Fig. S2), room temperature Mössbauer spectra (Fig. S3),
Mössbauer parameters (Table S1), combustion reaction equations
(eqn (S1 to S5)), standard formation enthalpy of materials (Table
S2), EDX spectra (Fig. S4), and elements analysis results (Table S3).
See DOI: 10.1039/c2cy00485b
from nonpolar oils into polar extractants, including water,9
acetonitrile,10 or ionic liquids (ILs).11 Hirai and Shiraishi et al.
conducted numerous studies on the photochemical desulfurization
for light oils by combining ultraviolet (UV) irradiation and
liquid–liquid extraction. Their works include the study on product
identification and the effect of photosensitizer benzophenone
on sulfur removal.12–16 To improve sulfur removal, researchers
also used TiO2 as photocatalyst17–22 because of its nontoxicity,
chemical and photochemical stability, low cost, and excellent
photocatalytic activity.23,24
Above mentioned studies were all performed by UV light
irradiation because the sulfur-containing compounds cannot
be photodegraded itself under visible light. Another reason is
that the photocatalyst TiO2 also can only absorb UV light
(l o 387 nm), which accounts for only a small fraction (3–5%)
of the energy of the sun, because of its wide band gap of
3.2 eV.25,26 Due to the difficulty of desulfurization under UV
light in industry, Shiiraishi et al.27 investigated the visible light-
induced DBT desulfurization using 9,10-dicyanoanthracene
(DCA) as photosensitizer. However, during experimentation,
the expensive DCA was dissolved in both oil and extractants,
and required recovery by subsequent reextraction or adsorp-
tion processes. Using photocatalysts with narrow band gaps
that can absorb visible light is a simple approach to desulfurize
under visible light irradiation. For instance, the single crystal

This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1455–1462 1455

of a-Fe2O3 has been used as a photocatalyst in the visible
region.28–31 Such photocatalysts, however, has the disadvantage
of a high recombination rate of photo-generated electrons and
photo-generated holes, which reduces their photocatalytic
efficiencies.
To prevent an electron–hole pair from recombining, hybrid
materials have been developed. An outstanding example is
Degussa P25 TiO2, which consists of B80% anatase and
B20% rutile, and displays high photocatalytic activity in the
UV region. Employing the synergistic effect of mixed phases
TiO2, Ye et al. prepared mixed phases of ilmentite- and
pyrochlore-type AgSbO3 which showed promising visible light
sensitive activity.32
Published on 24 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CY00485B
Fe2O3, including a-, b-, e-, and g-Fe2O3, is similar to TiO2
and AgSbO3. After thorough inquiry, there seems to be no
investigation conducted yet on the photocatalytic activity of
mixed-phase Fe2O3. The present study considered mixed-
phase Fe2O3 with a- and b- structures, obtained by solution
combustion, as candidates for visible light-induced photo-
catalyst. Solution combustion synthesis is a fast and easy
approach that allows the formation of homogeneous solid
solutions in preparing nanomaterials.33 Using this approach to
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synthesize iron oxides, ferric nitrate was used as the mother
salt, while urea, glycine, ammonium nitrate, or hydrazine were
used as fuels.34–38 Due to the nitrate and fuel having
an exothermic combustion reaction, the heat can cause the
formation of iron oxide nanopowders. Herein, we employed a
new fuel, triethylamine hydrochloride ((C2H5)3N
HCl), to
react with Fe(NO3)3 to obtain Fe2O3. The ratio of the
a-Fe2O3 in the mixed-phase Fe2O3 was primarily controlled
by the fuel addition.
The present study also investigated the photocatalytic oxidative
desulfurization of DBT through simulated sunlight irradiation
with mixed-phase Fe2O3. The relationship between the sulfur
removal and the ratio of a-Fe2O3/b-Fe2O3 were also examined
for development of the photocatalyst with higher activity.
Terephthalic acid fluorescence probing technique was used to
observe the formation of the  OH radicals during the photo-
oxidation process. The roles of radicals and hole scavengers on
the photocatalytic oxidation of DBT were also observed. A
major reaction pathway and visible light photocatalytic mechanism
were inferred according to the experimental results. The
current paper presents a highly effective approach in oxidizing
DBT under simulated sunlight. It also provides a new concept
for the development of visible-light-driven simple oxide photo-
catalyst with high activity.
2. Experimental
2.1. Preparation of catalysts
Fe(NO3)3
9H2O and (C2H5)3N
HCl were procured from Alfa
Aesar and used as received. A mixture of 0.01 mol of
Fe(NO3)3
9H2O and (C2H5)3N
HCl (0.002–0.004 mol) was
prepared and heated to ca. 80 1C for 2 min in air. Clear brown
aqueous concentrated salt solutions were then obtained, which
were still in liquid form at room temperature. The liquids were
then heated continuously up to 200 1C for 1 min in a tube
furnace with a heating rate of 10 1C min 1 and O2 flow rate of
1456 Catal. Sci. Technol., 2012, 2, 1455–1462
View Online
100 mL min 1. Finally, the products were obtained and taken
out, which were reddish-brown fine solid powders.
2.2. Characterization and analysis
Electrospray ionisation-mass spectrometry (ESI-MS) of solution
was performed on a Shimadzu 2010 EV LC-MS to validate the
solution structure. X-ray diffraction (XRD) patterns were
obtained on a Rigaku D/MAX 2500 X-ray diffractometer using
Cu-Ka radiation at a scanning rate of 0.021 s 1 for 2y from 101
to 801. XRD was employed to examine the iron oxide crystalline
structure and estimate crystal grain size. Mössbauer spectra
were measured by a Fast Comtec MA-250/mr-351 Mössbauer
spectrometer to determine the a-Fe2O3/b-Fe2O3 mass ratio.
The measurements were conducted at room temperature by a
57
Co(Pd) source. To examine the residue elements of the
samples after combustion, energy dispersive X-ray (EDX)
measurements were conducted on a JEOL JSM-6510 scanning
electron microscopy system equipped with an EDAX energy
spectrometer. The Brunauer–Emmett–Teller (BET) surface
area was measured using a Quantachrome NOVA2000 surface
area analysis meter. A Shimadzu IRPrestige 21 spectrometer
was employed to obtain Fourier transform infrared (FTIR)
spectra. The UV-visible diffuse reflection spectra (UV-Vis
DRS) were recorded using a Hitachi U-4100 spectrophotometer
in the range 200 nm to 800 nm at room temperature. To
measure the total Fe concentration, an AA240FS+AA240Z
Varian atomic absorption spectrometer was utilized. Sulfate
ions produced during the reactions, were examined using
ionic chromatography with a DIONEX DX 100 instru-
ment, equipped with an IonPacAS4A-SC Analytical Column
(4  250 mm). CO2 was identified by apparatus for measure-
ment of CO2.
2.3. Photocatalytic oxidative desulfurization
The photocatalytic reaction was performed in a photochemical
reactor (Fig. S1w). A quartz trap with a circulating water
jacket was placed in a glass vessel. To simulate solar radiation,
a 350 W Xe-lamp with light intensity of 7.86 W m 2 at 420 nm
was placed inside the quartz trap. Water was introduced
through the water jacket to cool the lamp and solution during
reaction. A glass vessel with an inlet tube for air entry and an
outlet tube for air and gaseous products release was placed
outside the jacket. The model oil for photocatalytic reaction
was prepared by dissolving DBT in n-octane with 500 mg mL 1
sulfur content. The given amount of catalyst and 50 mL of
model oil or actual diesel oil (478 mg mL 1 S) were mixed with
50 mL of water in the vessel. The mixed solution was photo-
irradiated for 0 min to 90 min with air bubbling (150 mL min 1).
Air exiting the outlet was introduced into distilled water or a
clear Ca(OH)2 solution. The reaction system cannot be stirred
using a magnetic stirrer because mixed-phase Fe2O3 has
magnetism properties. Thereby, the effect of air bubbling
was not only to dissolve O2 in the water, but also to blend
the solution. For comparison, the photocatalytic activity of
commercial P25 TiO2 purchased from Degussa was also measured
following the same procedure. The total sulfur content of the
samples was determined by a micro coulometer.
This journal is c The Royal Society of Chemistry 2012
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3. Results and discussion Table 1 Physical properties of the Fe2O3 samples

3.1. ESI-MS spectra of solution 0.3(C2H5)3NHCl
Fe(NO3)3 Phase XRD

composition/ crystallite
Fig. S2w shows the ESI-MS spectra of solution 0.3(C2H5)3NHCl
wt% size/nm BET
Molar ratio surface Band
Fe(NO3)3. Intensive peaks in the positive ion spectrum at of fuel to b-Fe2O3 a-Fe2O3 area/ gap/
m/z 102 and 266 correspond to (C2H5)3NH+ and [(C2H5)3NH+]- Sample Fe(NO3)3 b-Fe2O3 a-Fe2O3 d(211) d(110) m2 g 1 eV
(NO3 )[(C2H5)3NH+], respectively. Peaks at m/z 250, 277, and 304 F0 0.20 amorphous
are observed in the negative ion spectrum, which correspond to F1 0.25 57.0 43.0 42.5 43.9 55.6 1.84
Fe(NO3)2Cl2 , Fe(NO3)3Cl , and Fe(NO3)4 , respectively. The F2 0.30 36.6 63.4 43.1 45.3 49.5 1.82
hypergolic ability of nitrogen-containing salts have been proved by F3 0.35 16.2 83.8 44.2 46.1 41.6 1.85
F4 0.40 12.1 87.9 45.6 53.7 32.2 1.97
previous researchers.39,40 The ionic structure also ensures the
stability and the homogeneity of the obtained mixture.
associated with heat release. Combustion reactions are represented
Published on 24 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CY00485B

3.2. XRD, Mössbauer spectra, BET surface area
measurements, and EDX spectrometry
When the solutions x(C2H5)3NHCl
Fe(NO3)3 (x = 0.2 0.4)
were heated continuously until the liquids boiled, a flame
emerged, smoke was emitted, and powders were obtained.
These solutions were stable liquid systems and homogeneity
was achieved simply because the solutions were mixed using an
ionic scale. This process ensures the formation of homo-
geneous solid materials. As the solutions were being combusted,
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in proposed eqn S1 to S5.w Herein, the enthalpy change of
standard reactions (DH1, 298.15 K) are 80.12, 273.39,
466.66, 659.93, and 853.20 kJ mol 1 using the data of
standard formation enthalpy listed in Table S2.w
Previous studies42,43 indicated that b-Fe2O3 transformed to
a-Fe2O3 within 400 1C to 600 1C, which depended on the
crystallite size. In the current research, with the increase of the
fuel and the corresponding heat release, more b-Fe2O3 became
a-Fe2O3, and the crystallite size increased, including reductions

large amounts of gaseous products were quickly emitted from
the system, which prevented the combination of the obtained
materials and facilitated the formation of nanopowders. Fig. 1
presents the XRD patterns of these samples. There are mainly
amorphous products when the fuel was low (x = 0.2, sample
F0). When the fuel addition was increased, the obtained
samples F1, F2, F3, and F4 displayed structural characteristics
with mixed rhombohedral a-Fe2O3 (space group: R3c; JCPDS
No. 89-0596) and cubic b-Fe2O3 (space group: Ia3; JCPDS
No. 39-0238) phases. No peaks from other iron oxide phases,
such as g-Fe2O3 and Fe3O4, were found.
Fig. S3w presents the Mössbauer spectra of samples and the
Mössbauer parameters are shown in Table S1.w The doublet
and sextet are attributed to b- and a-Fe2O3, respectively.41 The
phase composition of b/a-Fe2O3 ratio measured from the
Mössbauer parameters is also shown in Table 1. Besides this,
Table 1 shows the crystallite size measured from XRD data
using Scherer equation and BET surface area of all the
samples. It was obvious that the b/a-Fe2O3 ratio have
decreased with the increase in the fuel addition. The cause is
in the BET surface area.
The elements were examined by EDX technique because the
solution combustion method typically produces residues in the
samples.44 Results of the EDX spectra and the elements
analysis are shown in Fig. S4 and Table S3.w From the spectra,
no N element was present in the samples, suggesting that the
combustion should be complete. The presence of Cl element in
the samples may likely be due to the HCl adsorbed in the
powders. With the increase of the additional (C2H5)3N
HCl
amount, the Cl element content also increased. The large amount
of C element may be due to the pollution of conductive adhesive
used in the test or the residual fuel.
3.3. FTIR spectroscopy
EDX analysis can not exclude the presence of residual carbon
moieties, for this reason we have performed a FTIR analysis of
the solids in order to determinate the presence of carbonaceous
species on the solid. As shown in Fig. 2, the vibration bands at
around 548 cm 1 and 470 cm 1 correspond respectively to the
lattice vibration of Fe–O stretching in a-Fe2O345 and b-Fe2O3.46
It is seen that the intensity of the peak at 548 cm 1 increased
and that of the peak at 470 cm 1 decreased, indicating the
change of the b/a-Fe2O3 ratio, which is consistent with
XRD and Mössbauer measurements. The absorption band
at 1636 cm 1 is attributed to free or crystal water. The
common peak at 2361 cm 1 may be due to the proliferation
of the IR beam through air.47 Peaks of potential undecomposed
groups, including NO3 and alkyl, were not detected. This also
suggests that combustion was almost finished.

3.4. Effect of b/a Fe2O3 ratio on the sulfur removal of DBT

Fig. 1 XRD patterns of Fe2O3 samples.
When 50 mL of model oil and an equal volume of water were
mixed for 5 min, sulfur removal was 8.5% without photo-
irradiation. This indicates that some DBT were extracted from
the nonpolar oil phase to the polar water phase. When the
0.05 g of Fe2O3 was introduced into the system, the sulfur

This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1455–1462 1457

Published on 24 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CY00485B
Fig. 2 FTIR spectra of samples (a) F1, (b) F2, (c) F3, and (d) F4.
removal was 8.9% after 90 min, which is attributed to the
DBT adsorption on the Fe2O3 surface. If the light was turned
on, DBT can be oxidized, while the remaining DBT in
n-octane phase was further extracted into the water phase.
Fig. 3 shows the effect of the various Fe2O3 on the DBT
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sulfur removal after photoirradiation for 90 min in the system
with V(H2O) : V(oil) = 1 : 1. The sulfur removal of DBT with
sample F4 containing only 12.1% b-Fe2O3 was only 48.5%,
while the visible light photocatalytic efficiency of the samples
increased with the increase of b-Fe2O3 content in the mixed-
phase. When the b-Fe2O3 content exceeded 36.6%, a slight
decrease of the photocatalytic efficiency was observed. There-
fore, sample F2 with 36.6% b-Fe2O3 and 63.4% a-Fe2O3
exhibited the highest photocatalytic effect with the sulfur
removal of 92.3%.
The UV-Vis DRS was measured because the UV-Vis absorp-
tion edge is related to the energy band gap of a semiconductor
catalyst. From Fig. 4, the four Fe2O3 photocatalysts have
noticeably similar and strong visible light absorption capabilities.
The band gaps of these photocatalysts can be identified by the
following equation: a(hn) = B(hn Eg)1/2, where a represents
the absorption coefficient, h is Planck’s constant, n is light
frequency, and B is an energy-independent constant.48 Based
on the equation, the band gaps of the samples can be deduced
from the tangent lines that are extrapolated to (a(hn))2 = 0.
Fig. 3 The sulfur removal of DBT with Fe2O3 samples. Reaction
conditions: model oil = 50 mL, water = 50 mL, t = 90 min, Fe2O3
amount = 0.05 g, room temperature.
1458 Catal. Sci. Technol., 2012, 2, 1455–1462
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Fig. 4 UV-Vis DRS of Fe2O3 samples.
Results are shown in Table 1. The small band gap is seen to
correspond to high photocatalytic activity.49 Conversely, while
the light absorption of sample F3 in the wavelength ranging
from 350 nm to 560 nm was evidently higher than that of
others, it did not exhibit the highest activity. This suggests that
other factors influence photocatalytic efficiency.
3.5. Photocatalytic desulfurization mechanism over mixed-
phase Fe2O3
In the semiconductor photocatalytic process, photoinduced
active species, including trapped hole (h+),  OH radical, and
superoxide anion (O2 ), were considered as the main oxidizing
species. Terephthalic acid fluorescence approach, which facilitates
the detection of  OH radical species, was employed in the present
study because terephthalic acid can react with  OH to form
highly fluorescent 2-hydroxyterephthalic acid that can be
detected by fluorescence spectroscopy.50 As shown in Fig. 5,
the intensity of the peaks with F2 gradually increased over
time, indicating that the free  OH radical may likely be the
main active species. To further validate the function of  OH,
h+, and O2 , the experiments were performed in the presence
of radical scavengers. Herein, KI, CH3OH, and 1,4-benzoquinone
(BQ) were employed as the scavengers for h+,  OH, and O2 ,
respectively.51–53
Fig. 6 shows that the addition of 2 mM of KI slightly improved
the sulfur removal, suggesting that h+ radicals were not the
primary oxidative species involved in this process. They also did
not cause the photooxidation of DBT. Since KI was utilized as h+
Fig. 5  OH radical trapping fluorescence spectra on terephthalic acid
solution with F2. Reaction conditions: terephthalic acid solution =
100 mL, terephthalic acid concentration = 2 mM, Fe2O3 amount =
0.05 g, room temperature.
This journal is c The Royal Society of Chemistry 2012
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scavenger to minimize the h+ and electron (e ) recombination,

the introduction of KI would have caused more electrons to
survive from the recombination.54 This enabled them to form
other oxidative species that caused the DBT degradation.
Conversely, the sulfur removal appeared to have been reduced
from 89.6% to 48.4% and 15.6% after 80 min by the addition of
2 mM of BQ and 50 mM of CH3OH, which acted as  OH and
O2 radical scavengers, respectively. This indicates that  OH
and O2 are the main oxidative species. To further examine the
influence of oxygen, N2 was added instead of air for 30 min
during illumination. The sulfur removal of the model diesel was
8.3%, which was almost the same as the extraction yield,
suggesting the need for oxygen in DBT photocatalytic degrada-
Published on 24 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CY00485B

tion. When air was introduced, the sulfur removal was 8.8% in Fig. 7  OH-trapping fluorescence spectra of various Fe2O3 samples
the absence of Fe2O3. This suggests the DBT could not be in a terephthalic acid solution. Reaction conditions: terephthalic acid
oxidized by a singlet oxygen (1O2) excited by O2. O2 acted not solution = 100 mL, terephthalic acid concentration = 2 mM, Fe2O3
only as reactant, but also as an electron scavenger, which amount = 0.05 g, room temperature.
minimized the recombination of photogenerated hole–electron
pairs, and thus improved the photocatalytic efficiency.55
To examine the cause for the difference of the sulfur removal
using different photocatalysts, the order of  OH concentra-
tions among the samples is shown in Fig. 7. The order of  OH
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concentrations was F2 4 F1 4 F3 4 F4, which is consistent

with the order of photocatalytic activities of these samples.
Fig. 7 shows that F2 had the highest separation efficiency of
electron–hole pairs because of its appropriate b/a-Fe2O3 ratio
and energy band structure. This occurrence can be described
based on the models of other mixed-phase materials, such as
TiO256,57 and AgSbO3,32 which have a similar energy band
structure. Scheme 1 presents the proposed charge separation
mechanism for mixed-phase Fe2O3. This is based on the band
gaps of b- and a-Fe2O3 (about 1.7 eV to 2.0 eV and 2.1 eV to
2.2 eV, respectively58) and a previously proposed model.32
Electron transfer from the a-Fe2O3 conductive band (CB) to
the b-Fe2O3 CB can effectively separate the photo-generated
electrons and holes, which thereby reduces their recombina-
tion. The a-Fe2O3-originating holes will then move from the
valence band (VB) of a-Fe2O3 to b-Fe2O3 phase and then react
with OH to form  OH radical to participate in the oxidation
reaction.56 However, when the b-Fe2O3 phase content
exceeded 36.6%, photocatalytic activity slightly decreased
because its band gap is narrower than that of the a-Fe2O3
phase and the recombination rate of the electron–hole pairs
Scheme 1 The proposed photoexcitation mechanism of Fe2O3 with
two-phase structure
during the b-Fe2O3 phase is faster than that in the a-Fe2O3
phase. This phenomenon is similar to that in P25 TiO2.
3.6. Photocatalytic desulfurization products with mixed-phase
Fe2O3
To verify the photooxidation products of DBT, the air of the outlet
was introduced into distilled water. Its pH was 6.89 prior to the
reaction, which went down to 3.51 after reaction. This was almost
similar to the pH of saturated H2CO3 at 298 K (3.49). When
KMnO4 solution was added into the water, the KMnO4 did not
fade, suggesting the absence of SO2 in the DBT products. When
the outlet of air was added into a clear Ca(OH)2 solution, the
solution became turbid. When the outlet was introduced to
apparatus for measurement of CO2, the apparatus showed that
the flow of CO2. Therefore, CO2 was one of the final products.
When BaCl2 solution was introduced into the lower layer
water after reaction, a white precipitate has formed, which
HCl could not be dissolved. This shows that SO42 was
present in the water. Ion chromatography also validated the
presence of SO42 . The obtained final products of CO2 and
SO42 agree with the results of Vargas et al.20

3.7. The influence of Fe2O3 amount on the sulfur removal of

DBT and its kinetics
Fig. 6 Effects of radical scavengers on the sulfur removal of DBT Fig. 8 presents the effect of photocatalyst Fe2O3 F2 amount on
over F2 photocatalyst. sulfur removal of DBT. The DBT removal at 90 min increased

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from around 81% with a dosage of 0.025 g Fe2O3 to
92.3–93.1% with 0.05–0.075 g Fe2O3; then slightly decreased.
This can be explained in terms of the availability of active sites
on the Fe2O3 surface and the light penetration into the
reaction system. As the availability of active sites increases,
the catalyst amount also increases.59 At higher catalyst
amount, light scattering by photocatalyst particles and
reduction of the light penetration reduce the light absorption
inside the solution.60 As shown in Fig. 8, the optimum Fe2O3
amount is 0.05 g to prevent the use of unnecessary additional
catalyst.
To investigate the photooxidation kinetics of DBT, samples
(0.1 mL) were obtained from the oil phase and the sulfur
Published on 24 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CY00485B
content was measured every 10 min in the reaction process.
Based on previous studies,19–21 the photocatalytic oxidation
rates of sulfur compounds are described by a pseudo-first-order
kinetics. The sulfur content of the model gasoline will address
eqn (1):
ln(C0/Ct) = kt (1)
where C0 and Ct are respectively the sulfur content of model
gasoline at time zero and time t (min), t is the illumination
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time, and k is the reaction rate constant (min 1). A plot of
ln(C0/Ct) versus time represents a straight line, the slope upon
which linear regression equals the apparent first-order rate
constant. The half-life (t1/2 (min)) is measured using eqn (2),
which is derived from eqn (1) by replacing Ct with C0/2:
t1/2 = ln2/k = 0.693/k (2)
Fig. 9 presents the time-course variation of ln(C0/Ct).
Table 2 lists the calculated k, correlation coefficient r, and t1/2.
The k is 0.0287 min 1 and half-life t1/2 is only 24.15 min with
0.05 g of Fe2O3. By comparison, k is only 0.017 min 1 with
0.05 g P25 TiO2, showing the photocatalytic activity of F2
under simulated sunlight irradiation is about 17 times that of
P25. This suggests that the mixed-phase Fe2O3 is an effective
visible light photocatalyst.
3.8. Leaching of iron in water
Light-induced dissolution of iron oxides is a common issue
and has been explored in some studies.61–63 This process
Fig. 8 Effect of the Fe2O3 amount on the sulfur removal of DBT.
Reaction conditions: model oil = 50 mL, water = 50 mL, t = 90 min,
room temperature.
1460 Catal. Sci. Technol., 2012, 2, 1455–1462
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involves the following steps.61,62 (1) The CB electron generation
by photoexcitation of iron oxides (eqn (3)). (2) Trapping of
electron in the surface Fe(III) sites (Fe(III)surf) to Fe(II) (eqn (4)).
(3) Desorption of photochemically formed Fe(II) at the surface
of iron oxides (Fe(II)surf) into the solution (eqn (5)). The Fe(II)aq
can also be oxidized to Fe(III)aq in the solution.
FeIII2O3 + hn - ecb + hvb+ (3)
Fe(III)surf + ecb - Fe(II)surf (4)
Fe(II)surf - Fe(II)aq (5)
When 0.05 g of sample F2 was used as photocatalyst in 50 mL
water, the total Fe ion concentration was 3.4359 mg L 1 after
90 min reaction. The leaching of iron in water accounts for
ca. 0.49 at% of the used Fe2O3. This suggests that the Fe2O3 is
a type of a relatively stable photocatalyst.
On the other hand, the leaching Fe ions may be responsible
for the desulfurization of DBT. To identify its effect, 0.5 g of
nano a-Fe2O3 purchased from Aladdin was added into 50 mL
of water, irradiated by light for 90 min. Then the a-Fe2O3 was
removed through a 0.22 mm Millipore filter. The total Fe ions
concentration of obtained solution was 3.7985 mg L 1. This
solution was mixed with model oil and irradiated with air
flow rate of 150 mL min 1 for 90 min. The desulfurization
yield is 11.38%, which is slightly higher than the extraction
yield of 8.5%, indicating Fe ions have little contribution to the
desulfurization of DBT.
3.9. Photocatalytic desulfurization of actual diesel
To desulfurize actual diesel, the photocatalytic process was
employed. The sulfur content of the diesel can be reduced from
478 mg mL 1 to 44.5 mg mL 1 after 90 min. This corresponds
to 90.7% sulfur removal, which is lower compared with that of
the model oil. The result agrees with other photocatalytic
desulfurization research,11,15,16 where two conflicting factors
emerged. On one hand, the diesel contains two-ring aromatics,
such as naphthalene (NP), which subdues the photoreaction of
DBT since the triplet energy of NP is inferior than that of
DBT. The energy transfer from photoexcited DBT to ground-
state NP could possibly have taken place during the reaction.16
On the other hand, the photooxidation of alkyl-substituted
Fig. 9 Time-course variation of ln(C0/Ct). Reaction conditions: model
oil = 50 mL, water = 50 mL, t = 90 min, room temperature.
This journal is c The Royal Society of Chemistry 2012

Table 2 DBT degradation apparent pseudo-first-order rate constants
(min 1) and associated half time (min), obtained from the slope of the
ln(C0/Ct) vs. time plot
Fe2O3 amount (g) 0.025 0.05 0.075 0.10 0.125
1 22, 1100–1103.
k (min ) 0.0193 0.0287 0.0301 0.0276 0.0213
Correlation coefficient r 0.9925 0.9944 0.9929 0.9950 0.9933
t1/2 (min) 35.91 24.15 23.03 25.11 32.54
DBTs in actual diesel have continued faster than that for
nonsubstituted DBT.15 This is due to the increase in electron
density values for both DBTs and benzothiophenes (BTs)
along with the growing carbon number of the alkyl substituents.
Afterwards, DBTs and BTs with alkyl substituents of higher
Published on 24 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CY00485B
carbon number will be more easily desulfurized.64
Conclusions
Mixed-phase Fe2O3 photocatalysts were prepared through
solution combustion. With an increase in fuel, the b/a-Fe2O3
ratio decreases, the crystallite size increases, and the BET
surface area decreases. The mixed-phase Fe2O3 were employed
as photocatalyst to desulfurize DBT through simulated solar
Downloaded on 05 October 2012
irradiation. The highest photocatalytic effect was demon-
strated by Fe2O3 with 36.6% b-Fe2O3 and 63.4% a-Fe2O3.
The DBT sulfur removal in n-octane reached 92.3% with
90 min irradiation. The kinetics of photooxidative desulfuriza-
tion of DBT was a pseudo-first-order with an apparent
rate constant of 0.0287 min 1 and half-time of 24.15 min.
The sulfur content of actual diesel could be reduced from
478 mg mL 1 to 44.5 mg mL 1 at 90 min. The photocatalytic
desulfurization mechanism of DBT with mixed-phase Fe2O3
was also proposed.
Acknowledgements
We are grateful for the financial support from the National
Natural Science Foundation of China (Nos. 21076060 and
20806021), the Key Project of Chinese Ministry of Education
(No. 210018), the One-Hundred Outstanding Innovative
Talents Scheme of Hebei Province Education Department
(No. CPRC022), the Natural Science Foundation of Hebei
Province (No. B2009000678), and the Training Funds for
Talents Project of Hebei Province. We also thank Dr M. Liu
for Mössbauer measurements and analysis.
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